CN105219969A - Vanadium wastewater and tailings in vanadium extraction is utilized to extract the method for manganese metal - Google Patents

Abstract

The invention relates to a method for extracting manganese metal by utilizing vanadium precipitation waste water and vanadium extraction tailings, belonging to the technical field of metallurgy and chemical industry. The invention provides a method for extracting manganese metal by using vanadium precipitation wastewater and vanadium extraction tailings, which includes the following steps: (1) mixing the vanadium precipitation wastewater and vanadium extraction tailings, heating to 60-80°C, and performing solidification after stirring (2) adding a reducing agent to the first filtrate to reduce the pentavalent vanadium in the solution to tetravalent vanadium, and then filtering to obtain the second filtrate; (3) adding an oxidizing agent to the second filtrate React at 50-60°C to oxidize the unreacted reducing agent in step 2; (4) add suspended solids or suspended particles in the activated carbon or polyacrylamide adsorption solution, then stir evenly and filter to obtain the third filtrate; (5) ) adding selenium dioxide or sulfurous acid to the third filtrate for electrolysis to obtain metal manganese and electrolytic anolyte. The invention provides a method for effectively recovering manganese resources in vanadium precipitation waste water and vanadium extraction tailings.

Description

Method for extracting metal manganese by utilizing vanadium precipitation wastewater and vanadium extraction tailings

technical field

The invention relates to a method for extracting manganese metal by utilizing vanadium precipitation waste water and vanadium extraction tailings, belonging to the technical field of metallurgy and chemical industry.

Background technique

In the clean production process of vanadium oxide, the vanadium slag extracted from the converter is used as raw material, and the vanadium oxide product is produced by calcification roasting-sulfuric acid leaching-acid ammonium salt vanadium precipitation process. This process technology solves the problem that the existing sodium salt roasting-water leaching-acid ammonium salt vanadium precipitation process leaching tailings and solid waste sodium sulfate produced by wastewater treatment are difficult to handle, and has the advantage of low wastewater treatment cost. Since the vanadium slag used in the production of vanadium oxide contains not only vanadium, but also a large amount of manganese, after iron removal, roasting, leaching and other processes, about 20-30% of the manganese in the raw material "vanadium slag" will enter the solution together with the vanadium Among them, most of them remain in the vanadium extraction tailings and piled up in the slag yard. In the precipitation process, the vanadium in the solution is enriched and recovered in the form of ammonium polyvanadate, while manganese exists in the vanadium precipitation wastewater, and its concentration is about 8-15g/L.

Aiming at the vanadium deposition wastewater produced by the calcification and roasting process, the patent CN102838233A uses lime milk to adjust the acidic vanadium deposition wastewater to alkaline, and then separates the solid and liquid to obtain an alkaline solution and gypsum slag; adding a decalcifying agent to the alkaline solution for decalcification , and then carry out solid-liquid separation to obtain the supernatant and decalcified slag; adjust the pH value of the supernatant to 3-7 with sulfuric acid, and then return to the leaching process for recycling. The method realizes the recycling of wastewater, can effectively control the concentration of calcium ions in the solution returned to the leaching process, and avoids the formation of calcium sulfate precipitation, but a large amount of manganese resources in the wastewater have not been effectively recovered, and the ore utilization rate is low.

For the vanadium-precipitated wastewater produced by the sodium roasting process: the patent CN102051486A uses the vanadium-precipitated wastewater as a leaching agent for vanadium-containing clinker, and uses the ammonium ions and phosphate ions contained in it to form a complex precipitate with magnesium ions, and then adds Phosphorus agent is used for deep phosphorus removal to produce low-phosphorus vanadium liquid, which realizes the reuse of vanadium precipitation wastewater; patent CN101812593A uses acid wastewater to clean vanadium extraction tailings, and then reduces, neutralizes, evaporates and concentrates to reduce The amount of alkali used for neutralization in the wastewater treatment process.

In the above patents, the manganese resources in the vanadium precipitation wastewater and the vanadium extraction tailings are not recycled.

Contents of the invention

In view of the current situation, the purpose of the present invention is to provide a way to effectively recover manganese resources in vanadium precipitation wastewater and vanadium extraction tailings, so as to realize the rational utilization of waste resources in the production process of vanadium oxide.

Technical scheme of the present invention:

The invention provides a method for extracting manganese metal by utilizing vanadium precipitation wastewater and vanadium extraction tailings, comprising the following steps:

(1) Mix the vanadium precipitation waste water with the vanadium extraction tailings, adjust the pH of the system to 1.5-2.5, then heat to 60-80°C, stir and react for 1-3 hours, then perform solid-liquid separation to obtain the first filtrate and residue; among them, The liquid-solid ratio of vanadium wastewater to vanadium extraction tailings is 0.6-1.0:1;

(2) adding a reducing agent to the first filtrate to reduce the pentavalent vanadium in the solution to tetravalent vanadium, adjusting the pH of the solution to 6.0 to 6.5, and then filtering to obtain the second filtrate;

(3) Add oxidant to the second filtrate, feed air, react at 50-60°C for 1-2h to remove unreacted reducing agent in step 2; wherein, the oxidant is manganese dioxide, hydrogen peroxide or persulfuric acid Ammonium;

(4) Then adjust the pH of the solution to 6.5 to 7.0, add activated carbon or polyacrylamide to absorb the suspended solids or suspended particles in the solution, then stir evenly and filter to obtain the third filtrate; the purpose of adding activated carbon here is to absorb in the solution The flocculent suspended matter or suspended particles, the suspended matter is mainly the precipitate produced by hydrolysis after ferrous ions are oxidized to ferric ions, and a small amount of silicate colloid in the solution; here, in addition to activated carbon, flocculation can also be added agent polyacrylamide;

(5) Adding selenium dioxide or sulfurous acid to the third filtrate for electrolysis to obtain metal manganese and electrolytic anolyte. The selenium dioxide or sulfurous acid added here is an additive for electrolytic manganese extraction.

The vanadium precipitation wastewater and vanadium extraction tailings are wastewater and waste tailings obtained in the process of producing vanadium oxide by calcification roasting or sodium roasting.

Preferably, the vanadium precipitation wastewater and vanadium extraction tailings are wastewater and waste residues produced in the calcification roasting vanadium extraction process.

Further, the vanadium precipitation wastewater meets: Mn8-20g/L, V0.05-0.3g/L, P0-0.02g/L, Fe0.05-0.2g/L, Ca0.8-1g/L, Mg4- 10g/L, NH ₄ ⁺ 8-15g/L, SO ₄ ^2- 85-120g/L, Si0.5-1.0g/L, pH1.5-3.0.

Further, in step 1, an acidity regulator is used to adjust the pH value. The acidity regulator is a mixture of sulfuric acid and electrolytic anolyte, and its [H ⁺ ] concentration is 1-3 mol/L. The electrolytic anolyte is from step 5.

Further, in step 2, the reducing agent is ferrous sulfate, sulfurous acid or iron filings, the molar ratio of the reducing agent to vanadium is 1.0-3.5:1, the reduction temperature is 60-80° C., and the reduction time is 40-90 minutes.

Further, in step 2, ammonia water is used to adjust the pH value of the solution.

Further, in step 3, the amount of the oxidant added is 0-2.5 g/L of the second filtrate (that is, the amount of the oxidant added per L of the second filtrate is 0-2.5 g).

Further, in step 4, the amount of activated carbon added is 0.5-2.5 g/L of the second filtrate, and the amount of polyacrylamide added is 5-20 mg/L of the second filtrate.

Further, in step 4, ammonia water is used to adjust the pH value of the solution.

Further, in step 5, the amount of selenium dioxide added is 0.025-0.035 g/L of the third filtrate, and the amount of sulfurous acid added is 0.01-0.04 g/L of the third filtrate.

Further, in step 5, the current density during electrolysis is 200-300A/m ² .

In step 5, the pH of the obtained electrolytic anolyte is 0.5-1.5.

Further, the electrolytic anolyte obtained in step 5 is returned to the calcified clinker leaching process for recycling or returned to step 1 as an acidity regulator to adjust the pH value of the system.

Beneficial effects of the present invention:

The technical problem to be solved by the present invention is to provide a method for extracting manganese metal by utilizing vanadium precipitation wastewater and vanadium extraction tailings. The manganese in the manganese is recycled in the form of metal manganese, which provides a new way for the comprehensive utilization of vanadium extraction tailings and waste water; realizes the rational utilization of waste resources in the production process of vanadium oxide.

Description of drawings

Fig. 1 is a process flow diagram of the present invention.

detailed description

The invention provides a method for extracting manganese metal by utilizing vanadium precipitation wastewater and vanadium extraction tailings, comprising the following steps:

(1) Mix the vanadium precipitation wastewater and the vanadium extraction tailings according to a certain liquid-solid ratio, use an acidity regulator to adjust the pH of the system to 1.5-2.5, heat the solution to 60-80°C, stir for 1-3 hours, and then carry out solid-liquid separation , to obtain the first filtrate and residue;

(2) adding a reducing agent to the first filtrate to reduce the V(V) in the solution to V(IV), adjusting the pH of the solution to 6.0-6.5 with ammonia water, and filtering to obtain the second filtrate;

(3) Add oxidant (manganese dioxide) to the second filtrate, feed air, and react at a constant temperature for 1 to 2 hours;

(4) Using ammonia water to adjust the pH of the solution to 6.5-7.0, adding activated carbon, stirring evenly and filtering to obtain the third filtrate;

(5) Add selenium dioxide or sulfurous acid to the third filtrate, carry out electrolysis operation, obtain metal manganese and electrolytic anolyte;

(6) The electrolytic anolyte is returned to the calcified clinker leaching process for recycling or returned to step (1) as an acidity regulator.

The specific implementation of the present invention will be further described below in conjunction with the examples, and the present invention is not limited to the scope of the examples.

Example 1

Take 5000mL of vanadium precipitation wastewater (containing manganese 10.20g/L, vanadium 0.25g/L, pH=1.5), add vanadium extraction tailings 5000g (containing manganese 4.82%, vanadium 1.24%), start stirring, and use acidity regulator ([ H ⁺ ]=1mol/L) to adjust the acidity of the system to 2.5, heated to 80°C in a water bath, stirred and reacted for 2 hours, and filtered to obtain the first filtrate (containing manganese 12.30g/L, vanadium 0.39g/L) and residue (containing manganese 2.58% , vanadium 1.03%); in the first filtrate, add ferrous sulfate 3.0g/L in the first filtrate, stir reaction 80min under 70 ℃, adopt ammoniacal liquor to adjust pH to 6.0 after reaction finishes, carry out solid-liquid separation to obtain the second filtrate and Vanadium-containing slag ( _16.2 % as _V2O5 ); add manganese dioxide solid 2g/L second filtrate to the second filtrate, feed air, and react at 60°C for 1.5h; use ammonia water to adjust the pH to 7.0, Add activated carbon 1.0g/L second filtrate, filter after stirring to obtain the third filtrate (containing manganese 12.40g/L, vanadium 0.005g/L); add selenium dioxide 0.02g/L in the third filtrate, pass into direct current , carry out electrolysis operation, the current density is 200A/m ² , and obtain 45.1g of metal manganese (product purity is 99.90%) and anolyte (containing manganese 2.40g/L, pH=1.0).

Example 2

Take 5000mL of vanadium precipitation wastewater (containing manganese 8.30g/L, vanadium 0.20g/L, pH=2.0), add vanadium extraction tailings 7500g (containing manganese 4.82%, vanadium 1.24%), start stirring, and use acidity regulator ([ H ⁺ ]=2mol/L) to adjust the acidity of the system to 1.5, heated to 70°C in a water bath, stirred and reacted for 1.5h, and filtered to obtain the first filtrate (containing manganese 12.20g/L, vanadium 0.61g/L) and residue (containing manganese 2.05 %, vanadium 0.92%); adding mass concentration to the first filtrate is 6% sulfurous acid 9.0mL/L the first filtrate (that is, adding 9ml sulfurous acid in the first 1L filtrate), stirred and reacted for 40min at 60°C, and the reaction was completed Finally, use ammonia water to adjust the pH to 6.0, carry out solid-liquid separation to obtain the second filtrate and vanadium-containing slag (24.4% as V ₂ O ₅ ); pass air into the second filtrate, and react at 60°C for 1 hour; use ammonia water to adjust pH to 6.5, add gac 2.0g/L second filtrate, filter after stirring to obtain the third filtrate (containing manganese 12.30g/L, vanadium 0.002g/L); Sulfuric acid (the mass ratio of sulfur dioxide in the sulfurous acid solution to the mass of the whole mixture is 6%), the amount of sulfurous acid added is 1L of the third filtrate, add 3mL of sulfurous acid, feed direct current, and carry out electrolysis operation, the current density is 250A/m ² 44.6g of manganese metal (product purity: 99.93%) and anolyte (containing manganese 2.75g/L, pH=1.5) were obtained.

Example 3

Take 5000mL of vanadium precipitation wastewater (containing manganese 14.50g/L, vanadium 0.30g/L, pH=2.5), add vanadium extraction tailings 6000g (containing manganese 5.74%, vanadium 1.42%), start stirring, and use an acidity regulator ([ H ⁺ ]=2mol/L) to adjust the acidity of the system to 2.0, heated to 60°C in a water bath, stirred and reacted for 3 hours, and filtered to obtain the first filtrate (containing manganese 18.20g/L, vanadium 0.56g/L) and residue (containing manganese 2.30% , vanadium 1.11%); add iron filings 2.5g/L (metal iron content is greater than 80% in the iron filings) in the first filtrate, stir reaction 80min under 70 ℃, adopt ammoniacal liquor to adjust pH to 6.5 after reaction is finished, carry out solid-liquid Separate the second filtrate and vanadium-containing slag (20.6% as V ₂ O ₅ ); add manganese dioxide solid 1.5g/L second filtrate to the second filtrate, pass in air, and react at 60°C for 1.0h; Adopt ammonia water to adjust pH to 7.0, add activated carbon 0.5g/L second filtrate, filter after stirring to obtain the third filtrate (containing manganese 18.32g/L, vanadium 0.006g/L); add selenium dioxide 0.025g/L in the third filtrate g/L of the third filtrate, feed direct current, and carry out electrolysis operation, the current density is 300A/m ² , to obtain 76.2g of manganese metal (product purity is 99.93%) and anolyte (containing manganese 2.20g/L, pH=0.5) .

The metal manganese components of the products obtained in Examples 1-3 are shown in Table 1, and the vanadium-containing slag obtained during the treatment process (the vanadium content is 15-25% as V ₂ O ₅ ) is returned to the main process.

Table 1 Product Manganese Composition

The advantages of this method are: (1) the manganese resources in the vanadium precipitation wastewater and vanadium extraction tailings are recovered in the form of metal manganese, and the purity of the product metal manganese reaches the national standard YB/T051-2003 general-purpose DJMnD standard; (2) the treatment The vanadium-containing slag produced in the process can be returned to the main process, and together with the converter vanadium slag, carry out calcification roasting-sulfuric acid leaching to extract vanadium, effectively recovering the vanadium in the vanadium precipitation wastewater and vanadium extraction tailings; (3) the anode obtained by the electrolysis operation The solution can be used in the acid leaching of calcified clinker, which can reduce the consumption of sulfuric acid in the leaching process.

Claims (10)

1. Utilize the method for extracting metal manganese from vanadium waste water and extracting vanadium tailings, it is characterized in that, comprises the steps: (1) Mix the vanadium precipitation waste water with the vanadium extraction tailings, adjust the pH of the system to 1.5-2.5, then heat to 60-80°C, stir and react for 1-3 hours, then perform solid-liquid separation to obtain the first filtrate and residue; among them, The liquid-solid ratio of vanadium wastewater to vanadium extraction tailings is 0.6-1.0:1; (2) adding a reducing agent to the first filtrate to reduce the pentavalent vanadium in the solution to tetravalent vanadium, adjusting the pH of the solution to 6.0 to 6.5, and then filtering to obtain the second filtrate; (3) Add oxidant to the second filtrate, feed air, react at 50-60°C for 1-2h to remove unreacted reducing agent in step 2; wherein, the oxidant is manganese dioxide, hydrogen peroxide or ammonium persulfate ; (4) Then adjust the pH of the solution to 6.5 to 7.0, add activated carbon or polyacrylamide to absorb suspended solids or suspended particles in the solution, then stir and filter to obtain the third filtrate; (5) Adding selenium dioxide or sulfurous acid to the third filtrate for electrolysis to obtain metal manganese and electrolytic anolyte. 2. according to claim 1, utilize the method for extracting manganese metal by vanadium precipitation waste water and vanadium extraction tailings, it is characterized in that, described vanadium precipitation waste water and vanadium extraction tailings are obtained in the vanadium oxide production process of calcification roasting or sodium roasting waste water and waste residue; preferably waste water and waste residue produced by calcification roasting vanadium extraction process; more preferably, the vanadium precipitation waste water meets: Mn8-20g/L, V0.05-0.3g/L, P0-0.02g /L, Fe0.05-0.2g/L, Ca0.8-1g/L, Mg4-10g/L, NH ₄ ⁺ 8-15g/L, SO ₄ ^2- 85-120g/L, Si0.5-1.0 g/L, pH1.5-3.0. 3. according to claim 1 or 2, utilize the method for extracting metal manganese from vanadium waste water and vanadium tailings, it is characterized in that, in step 1, an acidity regulator is used to adjust the pH value, and the acidity regulator is sulfuric acid and an electrolytic anode The mixed liquid of the acidity regulator has a [H ⁺ ] concentration of 1-3 mol/L, and the electrolytic anolyte is derived from step 5. 4. The method for extracting manganese metal by utilizing vanadium precipitation wastewater and vanadium extraction tailings according to any one of claims 1 to 3, characterized in that, in step 2, the reducing agent is ferrous sulfate, sulfurous acid or iron filings, and the reduction The molar ratio of agent to vanadium is 1.0~3.5:1, the reduction temperature is 60~80℃, and the time is 40~90min. 5. The method for extracting manganese metal by using vanadium precipitation wastewater and vanadium extraction tailings according to any one of claims 1 to 4, characterized in that, in step 2 and step 4, ammonia water is used to adjust the pH value of the solution. 6. The method for extracting manganese metal by utilizing vanadium precipitation wastewater and vanadium extraction tailings according to any one of claims 1 to 5, characterized in that, in step 3, the amount of oxidant added is 0 to 2.5 g/L of the second filtrate. 7. The method for extracting manganese metal by utilizing vanadium precipitation wastewater and vanadium extraction tailings according to any one of claims 1 to 6, characterized in that, in step 4, the amount of activated carbon added is 0.5 to 2.5 g/L second filtrate , the amount of polyacrylamide added is 5-20 mg/L of the second filtrate. 8. According to any one of claims 1 to 7, the method for extracting metal manganese by using vanadium precipitation wastewater and vanadium extraction tailings is characterized in that, in step 5, the amount of selenium dioxide added is 0.025～0.035g/L the third Filtrate, sulfurous acid addition is 0.01～0.04g/L third filtrate. 9. The method for extracting manganese metal by using vanadium precipitation wastewater and vanadium extraction tailings according to any one of claims 1 to 8, characterized in that in step 5, the current density during the electrolysis is 200 to 300 A/m ² . 10. The method for extracting manganese metal by using vanadium precipitation wastewater and vanadium extraction tailings according to any one of claims 1 to 9, characterized in that the electrolytic anolyte obtained in step 5 is returned to the calcified clinker leaching process for recycling or returns to the step 1 as an acidity regulator to adjust the pH value of the system.